Switching Selectivity in Borylative Allyl–Allyl Cross-Coupling through Synergistic Catalysis

A Cu/Pd-catalyzed borylative coupling of allenes with allyl carbonates is reported. Synergistic Cu/Pd catalysis enables a divergent selectivity compared to Cu catalysis and allows for the regio-, diastereo-, and enantioselective formation of synthetically versatile chiral borylated 1,5-dienes featur...

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Detalles Bibliográficos
Autores: Vázquez-Galiñanes, Nuria, Sciortino, Giuseppe, Piñeiro-Suárez, Martín, Tóth, Balázs L., Maseras, Feliu, Fañanás-Mastral, Martín
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universidad de Santiago de Compostela (USC)
Repositorio:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
Idioma:inglés
OAI Identifier:oai:minerva.usc.gal:10347/39822
Acceso en línea:https://hdl.handle.net/10347/39822
Access Level:acceso abierto
Palabra clave:Allyl Group
Inorganic Carbon Compounds
Palladium
Selectivity
Stereoselectivity
Descripción
Sumario:A Cu/Pd-catalyzed borylative coupling of allenes with allyl carbonates is reported. Synergistic Cu/Pd catalysis enables a divergent selectivity compared to Cu catalysis and allows for the regio-, diastereo-, and enantioselective formation of synthetically versatile chiral borylated 1,5-dienes featuring two adjacent tertiary stereocenters. DFT calculations support a closed inner-sphere SE2′ transmetalation between the catalytic allyl copper and allyl palladium intermediates and point at the reductive elimination of the resulting bis(allyl)Pd intermediate as the regio- and diastereo-determining step.